Cotton-oxime, cotton-semicarbazone, and cotton-hydantoin-textile products of high nitrogen content

ABSTRACT

Poly(methyl vinyl ketone)-cotton copolymers are prepared by graft copolymerization and subsequently reacted through abundant ketone groups thereby producing new cotton-oximes, cottonsemicarbazones, and cotton-hydantoins. The chemical modifications of the cotton textile products are permanent thereby permanently modifying the mechanism and rate of oxidation of cotton as desired in flame-resistant cotton textile products.

United States Patent [1 1 Portnoy et al.

[ Oct. 21, 1975 COTTON-OXIME, COTTON-SEMICARBAZONE, AND COTTON-HYDANTOIN-TEXTILE PRODUCTS OF HIGH NITROGEN CONTENT Inventors: Norman A. Portnoy, Parsippany,

N.J.; Alden H. Reine, New Orleans; Jett C. Arthur, Jr., Metairie, both of La.

Assignee: The United States of'America as represented by the Secretary of Agriculture, Washington, DC.

Filed: Apr. 6, 1973 Appl. No.: 348,558

Published under the Trial Voluntary Protest Program on January 28, 1975 as document no. B 348,558.

U.S. Cl 8/194; 8/196; 8/116 R;

8/DIG. l2; 8/DIG. 18 Int. Cl. D061 3/00 Field of Search 8/194, 196, DIG. 12,

S/DIG. 18,116 R, 116.4; 204/l59.12; 260/1174 GC [56] References Cited UNITED STATES PATENTS 3,138,564 6/1964 Borunsky 8/DIG. 18 3,254,939 6/1966 Munzel 8/DlG, 18

Primary Examiner-Stephen J. Lechert, Jr. Attorney, Agent, or Firm-M. Howard Silverstein; Max D. Hensley [57 ABSTRACT 7 Claims, N0 Drawings 'cot ton, as desired in flame-resistant cott on products.

This invention relates to a multi-step process for the preparation of nitrogenous cotton products wherein (1) a polyvinyl cotton copolymer product is prepared by a free-radical initiated copolymerization process to,

introduce permanently large concentrations of ketone groups in the cotton product and then (2) subsequent reactions of the ketorie groups of the cotton product to yield oximes, semicarbazones," and hydantoins of the cotton products, that is, nitrogenous products.

Themethod of this invention has as its objective the permanent modificationof cotton by the preparation of poly(methyl vinyl ketone)-cotton copolymers and subsequent reactions of the ketone groups to yield nitrogenous derivatives of cotton products.

In the flame-proofing of cotton products it is reported that treatments and/or chemical modification of cotton with chemical reagents, which contain nitrogen, boron, phosphorus, or bromine, generally produce cotton products with flame-resistant and/or flameretardant properties. One of the important problems of treatments of cotton by the usual dip-pad-dry-cure" process is that the treatment may be diminished or lost duringzsubsequent laundering and cleaning of cotton products, and consequently the flame-resistant and/or flame-retardant properties of the cotton products are reduced or lost. entirely. Chemical modification of cotton, so that a covalent linkage is formed between the chemical reagent and the cotton cellulose molecule, increases the permanency of the flame-resistant and/or flame-retardant properties which may be imparted to the cotton. However, due to the limited number of reactive sites on the cotton cellulose molecule, the extent of reaction is limited, particularly when the original natural fibrous structure is retained. Consequently, flame resistant and/or flame retardant properties imparted to'cotton by chemical modification are usually limited. v

The instant invention defines a process whereby cotton is (l) graft copolymerized with methyl vinyl ketone; and then (2) the ketone groups, contained in the grafted copolymer are reacted with nitrogenous reagents to yield oxirnes, semicarbazones, and hydantoins of cottoncellul oslc textile products. To accomplish this the fibrous cottonis demoisturized and then irradiated under a nitrogen atmosphere at about 23C by a source of high en erg'yiionizing radiation, such as; cobalt-60, to form trapped or long-lived free radicals within the cellulosic structures. (The radiation dosage'reco mmended .is about 5.25? electron volts per gram of cotton at which about one trapped free radical per molecule of cotton cellulose is formed and at whichi'textile quality fibrous cotton is retained.) The irradiated'fibrous cotton is transferred to reaction vessels using a dry-box under nitrogen atmosphere. The irradiated cotton is then immersed at 25C in solutions of methyl vinyl ketone in either water, methanol, N,N-dimethylformamide or combinations of water and one of the other solvents-for desired reaction times. The concentration of methyl vinyl ketone ranged from 9 volume-% to 25 volume-%; the concentrations of solvents were volume-% water, methanol, or N,N-dimethylformamide and ranged from combinations of water with either solvent from 0 to 100% volume-%; the reaction times ranged from 0 to 180 minutes with maximum reaction occurring at about minutes to yield the intermediate cotton textile products containing 6.3% to 53% of poly(methyl vinyl ketone). The yarns were subjected to the standard and other physical testing through every phase of the investigative work. Typical breaking strengths for the cotton yarns ranged from about 9.2 pounds for irradiated yarn to about 7.3 pounds for cottonpoly(methyl vinyl ketone) copolymer yarns containing 13% to 53% poly(methyl vinyl ketone).

Typical breaking strengths for the cotton-oximes ranged from-about 6.9 to 7.8 pounds for cottonpoly(methyl vinyl ketone) copolymer oximated yarns containing 7.5% to 34% poly(methyl vinyl ketone) thereby yielding non-rigid cellulosic textile products with high nitrogen content, good hand and breaking strength.

The most significantly inventive facet of theinvention starts at the point where samples of cottonpoly(- methyl vinyl ketone) copolymer yarns were heated, each sample separate from the other, in solutions of hydroxylamine-hydrochloride, semicarbazidehydrochloride, or potassium cyanide and ammonium carbonate to product fibrous cotton-oximes, cottonsemicarbazones, and cotton-hydantoins through quantitative reaction at the ketone group of the grafted copolymer as confirmed by nitrogen analyses and infrared spectral data. Specific details of this investigation were first disclosed in CARBOHYDRATE RESEARCH, Vol. 24 (1972), pp. 198-201, which is published by The Netherlands publisher Elsevier Publishing Com.- pany, Amsterdam, bearing the title Synthesis of Nitrogenous'Derivatives of Cellulose-Poly(methyl vinyl ketone) Copolymers. Oximes, Semicarbazones, and Hydantoins," by these same authors.

A Graphic Representation and Sequence of Reactions is here provided to assist the reader in the study of this invention. It should be noted that although in the preparation 'of the Textile Products of High Nitrogen Content one must follow the sequence of Phases l, ll and "I, only Phase III is the invention.

The products and process of this invention are unlike the nitrogen-containing textile products known to-date, including aminized cotton, urea-formaldehyde condensates, methylolmelamines, and melamineformaldehyde condensates, where resinous compounds may generally be occluded with or tied to primary hydroxyls of the cellulosic structure, and whereby to obtain products containing the nitrogen contents produced by the process of this invention, a degree of substitution, or occlusion of reactants required would result in a very boardy textile. Conversely, the products produced by the present invention while being of a greater nitrogen content, and are not boardy at all. For

consultation of these facts of the prior art attention is called to Cellulose and Cellulose Derivatives," N. M.

Bikales and L. Segal, eds., Wiley-lnterscience, New York, 1971, pp. 1,095-1,113,- 1,277-1,291, and 1,2931,33 1, these pages dealing respectively with durable press properties, ion-exchange characteristics, and fire retardance.

The following examples are provided to illustrate the invention and are not to be construed as limiting the invention in any manner whatever.

EXAMPLE 1 Four cotton-oxime samples were prepared and evalu-.

ated in this manner. Cotton-poly(methyl vinyl ketone) copolymer yarn samples, each weighing about 2 grams, were reacted with a solution containing 20 grams of ethanol, grams pyridine, and a quantity of hydroxyl amine hydrochloride 2.6 times the number of moles of ketone groups contained in the copolymer yarn (calculated from the composition of the copolymer yarn used). The copolymer yarns contained respectively 7.4%, 18%, 30%, and 45% of poly(methyl vinyl ketone). Each copolymer yarn was placed in a vessel with the exact same composition solution, and each refluxed at 82C and 760 torr for. 2 hours. Then each reacted cotton copolymer yarn was washed separately with water, and dried in an air stream at 60C for 1 hour. Quantitative reactions of the ketone groups of the cotton copolymer yarns formed the oximated yarns here described: 1) The cotton copolymer yarn containing 7.4% poly(methyl vinyl ketone) was oximated to a 1.49% nitrogen content; calculated for quantitatively oximated yarn was. 1.37% nitrogen. (2) The yarn containing 18% poly( methyl vinyl ketone) was oximated to a 3.15% nitrogen content; the calculated figure was 3.08% nitrogen.

(3) The yarn containing 30% was oximated to a 4.20% nitrogen content; the calculated figure was 4.46%. (4) The yarn containing 45% was oximated to a 5.77% nitrogen content; the calculated figure was 5.92%.

EXAMPLE 2 Three cotton-semicarbazone samples were prepared and evaluated in this manner. Cotton-poly(methyl vinyl ketone) copolymer yarn samples each weighing about 2 grams were reacted with, a solution containing 1 gram of sodium acetate, 25 grams of water, and a quantity of semicarbazide-hydrochloride 2.6 times the number of moles of ketone groups contained in the copolymer yarn (calculated from the composition of the copolymer yarn used). The copolymer yarns contained respectively 27%, and 35% of poly(methyl vinyl ke- 1 tone). Each copolymer yarn was placed in a vessel with the exact same composition solution, and each heated at 60C for 30 minutes, washed with water, and dried in an air stream at 60C for 1 hour. Less than quantitative reactions of the ketone groups of the cotton copolymer yarns to form semicarbazonated yarns were obtained. The results are: (l) The cotton copolymer. yarn containing 15% poly (methyl vinyl ketone) was semicarbazonated to a 5.89% nitrogen content; calculated for quantitatively semicarbazonated yarn was 7.15%.

(2) The yarn containing 27% poly(methyl vinyl ketone) was semicarbazonated to an 8.22% nitrogen content; the calculated figure was 10.94% nitrogen. (3)

6 The yarn containing 35% poly(methyl vinyl ketone) was semicarbazonated to a 10.14% nitrogen content; the calculated figure was 12.94% nitrogen.

EXAMPLE 3 Three cotton-hydantoin samples were prepared and evaluated in this manner. Cotton-poly(methyl'vinyl ketone) copolymer yarn samples each weighing about 2 grams were reacted with a solution containing 40grams of 50% aqueous ethanol and a quantity of potassium cyanide .2 times the moles of ketone groups contained in the copolymer plus a quantity of ammonium carbonate 4 times the moles of ketone groups (as before). The i copolymer yarns contained respectively 6.3%, 16%,

and 27% poly(methyl vinyl ketone). Each copolymer yarn was placed in a vesselwith the exact same composition solution, and each heated at C for 3 hours minutes), washed with water, and dried in an air stream at 60C for 1 hounLess than quantitative reactions of the ketone groups of the cotton copolymer semicarbazones, and cotton hydantoins were found to have breaking strength properties satisfactory for textile uses.

We claim: 1

l. A process for producing chemically modified nonrigid cellulosic textileswith high nitrogen content and good hand, the process comprising reacting cellulosepoly(methyl vinyl ketone) copolymer with a nitrogencontaining compound selected from the group consisting of hydroxyamine hydrochloride, semicarbazide hydrochloride, and potassium cyanide in the presence of 1 ammonium carbonate,

2. A. process for producing cellulose-oximes in the form of non-rigid textiles with high nitrogen content and good hand, the process comprising:

a. mixing 2 parts by weight of a fibrous'cellulose-.

poly(methyl vinyl ketone) copolymer with a solu-. tion containing about 20 parts by weight of ethanol, 5 parts by weight pyridine, and a quantity of hydroxylamine hydrochloride equivalent to about 1 2.6 times the number of moles of ketone groups contained in the copolymer, and

b. refluxing the mixture of (a) at about 82C. and 760 torr for about 2 hours to obtain quantitative yields.

of fibrous cellulose-oxime.

3. A process for producing cellulose-semicarbazones in the form of non-rigid textiles withhigh nitrogen content and good hand, the process comprising:

a. mixing 2 parts by weight of a fibrous cellulose-poly(methylvinyl ketone)c0po1ymer with a solution containing about 1 part of sodium acetate, 25 parts of water, and a quantity of semicarbazide hydrochloride equivalent to about 2.6 times the number of moles of ketone groups contained in the copolymer; and

b. heating the mixture of (a) sufficiently to obtain the fibrous cellulose-semicarbazone. I

6 4. A process for producing cellulose-hydantoin in the tone groups containedrin the copolymer; and form of non-rigid textiles with high nitrogen content b. heating the mixture of (a) sufficiently to obtain the and good hand, the process comprising: fibrous eellulose-hydantoin.

a. mixing 2 parts by weight of a fibrous cellulose- 5. The fibrous cellulose-oxime produced by the propoly(methyl vinyl ketone) copolymer with a solu- 5 cess of claim 2. tion containing about 40 parts of 50% aqueous eth- 6. The fibrous cellulose-semicarbazone produced by anol, and a quantity of potassium cyanide equivathe process of claim 3. lent to about 2 times the moles of ketone groups 7. The fibrous cellulose-hydantoin produced by the contained in the copolymer plus a quantity of amprocess of claim 4. monium carbonate about 4 times the moles of ke- 0 

1. A process for producing chemically modified non-rigid cellulosic textiles with high nitrogen content and good hand, the process comprising reacting cellulose-poly(methyl vinyl ketone) copolymer with a nitrogen-containing compound selected from the group consisting of hydroxyamine hydrochloride, semicarbazide hydrochloride, and potassium cyanide in the presence of ammonium carbonate.
 2. A PROCESS FOR PRODUCING CELLULOSE-OXIMES IN THE FORM OF NON-RIGID TEXTILES WITH HIGH NITROGEN CONTENT AND GOOD HAND, THE PROCESS COMPRISING: A. MIXING 2 PARTS BY WEIGHT OF A FIBROUS CELLULOSE-POLY(METHYL VINYL KETONE) COPOLYMER WITH A SOLUTION CONTAINING ABOUT 20 PARTS BY WEIGHT OF ETHANLO, 5 PARTS BY WEIGHT PYRIDINE, AND A QUANTITY OF HYDROXYLAMINE HYDROCHLORIDE EQUIVALENT TO ABOUT 2.6 TIMES THE NUMBER OF KETONE GROUPS CONTAINED IN THE COPOLYMER, AND B. REFLUXING THE MIXTURE OF (A) AT ABOUT 82*C. AND 760 TORR FOR ABOUT 2 HOURS TO OBTAIN QUANTITATIVE YIELDS OF FIBROUS CELLULOSE-OXIME.
 3. A process for producing cellulose-semicarbazones in the form of non-rigid textiles with high nitrogen content and good hand, the process comprising: a. mixing 2 parts by weight of a fibrous cellulosepoly(methyl vinyl ketone) copolymer with a solution containing about 1 part of sodium acetate, 25 parts of water, and a quantity of semicarbazide hydrochloride equivalent to about 2.6 times the number of moles of ketone groups contained in the copolymer; and b. heating the mixture of (a) sufficiently to obtain the fibrous cellulose-semicarbazone.
 4. A process for producing cellulose-hydantoin in the form of non-rigid textiles with high nitrogen content and good hand, the process comprising: a. mixing 2 parts by weight of a fibrous cellulose-poly(methyl vinyl ketone) copolymer with a solution containing about 40 parts of 50% aqueous ethanol, and a quantity of potassium cyanide equivalent to about 2 times the moles of ketone groups contained in the copolymer plus a quantity of ammonium carbonate about 4 times the moles of ketone groups contained in the copolymer; and b. heating the mixture of (a) sufficiently to obtain the fibrous cellulose-hydantoin.
 5. THE FIBROUS CELLULOSE-OXIME PRODUCED BY THE PROCESS OF CLAIM
 2. 6. The fibrous cellulose-semicarbazone produced by the process of claim
 3. 7. The fibrous cellulose-hydantoin produced by the process of claim
 4. 